WO1994013706A1 - Synthese directe par polymerisation cationique vivante de polymeres contenant de l'azote - Google Patents

Synthese directe par polymerisation cationique vivante de polymeres contenant de l'azote Download PDF

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WO1994013706A1
WO1994013706A1 PCT/US1993/011918 US9311918W WO9413706A1 WO 1994013706 A1 WO1994013706 A1 WO 1994013706A1 US 9311918 W US9311918 W US 9311918W WO 9413706 A1 WO9413706 A1 WO 9413706A1
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nitrogen
polymer
groups
group
polymerization
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PCT/US1993/011918
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English (en)
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Hervé Marcel CHERADAME
Frank Joung-Yei Chen
Jon Edmond Stanat
Hung Anh Nguyen
Behrooz Rajabali Tabar
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Exxon Chemical Patents Inc.
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Priority to EP94902515A priority Critical patent/EP0674663A1/fr
Publication of WO1994013706A1 publication Critical patent/WO1994013706A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts

Definitions

  • This invention relates to a method for direct synthesis, by living cationic polymerization, of nitrogen-containing polymers, and particularly to the production of nitrogen-containing polymeric materials in a single step Fhedel-Crafts polymerization of olefinic materials containing substantial amounts of isobutylene.
  • Living polymerizations are defined (page 32) as ideal living polymerization in which charge transfer and termination are absent, and quasi-living polymerizations as having rapidly reversible charge transfer and/or termination present wherein the rate of these processes is faster than that of propagation. In either case the living behavior of the polymer results in a polymer in which charge, transfer and termination are absent.
  • living polymers are therefore defined as polymers which have substantially and preferably no apparent chain transfer and termination.
  • Resulting polymers have low polydispersity indices (molecular weight distributions) of preferably less than 1.5 and in the range of 1.5 to the ideal value of 1 , where all of the molecular chains are of the same length.
  • Cationic living polymerization systems take place by the polymerization reaction of monomers in the presence of a cationic initiator.
  • a living polymerization system is one wherein the molar ratio of the monomer to initiator is equal to the degree of polymerization.
  • the calculated molecular weight therefore, equals the degree of polymerization times the molecular weight of the monomer plus the molecular weight of the initiator.
  • the measured number average molecular weight is equal to the calculated molecular weight, evidencing the absence of true termination.
  • Polymers particularly polyolefin substrates, having nitrogen-containing functional groups such as the azide, cyano, carbonylamino or thiocarbonylamino groups are useful since the functional group is polar, and imparts desirable properties to a polyolefinic substrate. Also, these groups may act as a reactive site for further modification of the polymer.
  • Nitrogen-containing polyisobutylenes have applications such as lube additives, compatibilizers, emulsifiers, and the like.
  • azide terminal polymers may be further modified by phthalamidation or reduction of the azide group producing useful polymer products.
  • Pseudohalogen or halogenoids include inorganic anions, e.g., CN “ , CNO " , CNS “ and N3 which have properties resembling those of halide ions as disclosed in Discher, Modern Inorganic Pharmaceutical Chemistry. John Wiley & Sons, Inc., N.Y., p. 343 (1964).
  • a polymer is derived from the monomer, using an initiator having nitrogen-containing function such as azide, cyano, carbonylamino or thiocarbonylamino group. Results such as these are referred to in U.S. Patent No. 5,032,653.
  • the polymeric products were not disclosed to have a narrow molecular distribution (i.e., monodispersed type).
  • the molecular weight was controlled by the monomer feed rate and the amount of Lewis acid catalyst as well as the monomer to initiator ratio.
  • the amount of initiator was based on a Lewis acid to initiator mole ratio of 3:1 to 1 :3 with enhanced results as the ratio approaches 1 :1.
  • the molecular weight distribution (MWD) is controlled based on monomer feed rate and product removal rate.
  • a method for the direct synthesis of polymeric materials functionalized with nitrogen-containing functional groups comprising the steps of providing a cationically polymerizable monomer, and initiating polymerization by the addition of a cationic polymerization catalyst, in the presence of a nitrogen-containing initiator compound having at least one nitrogen-containing functional group selected from -N3, -NCO, -OCN, -SCN, -CN and -NCS chemically bound to a release moiety, wherein the ratio of moles of catalyst to nitrogen-containing functional groups is greater than 3:1.
  • the resulting polymer is terminally substituted by the nitrogen-containing functional groups.
  • the present invention includes preferred initiator bis(1-azido-1- methylethyl)benzene and the method to prepare such preferred initiator.
  • the nitrogen-containing functional group is bound to a secondary or tertiary carbon atom of the release moiety.
  • Preferred nitrogen-containing initiators include hydrocarbyl compounds and silyl compounds, substituted with at least one nitrogen-containing group comprising azido (-N3), cyano (also referred to as nitrile) (-CN), isocyanato (carbonylamino) (-NCO), thiocarbonylamino (isothiocyanato) (-NCS), cyanato (-OCN), and thiocyanato (-SCN).
  • the polymerization catalyst is a Friedel-Crafts catalyst and the nitrogen-containing initiator and monomer are preferably admixed in the substantial absence of the Friedel-Crafts catalyst.
  • the process of the present invention is a "living polymerization".
  • the living polymer is achieved by polymerizing the monomer with a catalyst to initiator ratio of greater than 3.0:1 ; a most useful range of from 3.1 :1 to 30:1 , and more specifically 4:1 to 30:1 and 6:1 to 20:1.
  • Mw/Mn narrow molecular weight distribution
  • the polymer made by the claimed process has as a terminal group the nitrogen-containing functional group.
  • the molecular weight can be varied and can range from 300 or lower to 15,000,000 or higher with a specific range of from 300 to 15,000,000 and preferred ranges depending upon use.
  • An advantage of the polymerization method of the present invention is that the functionalization is obtained directly from the mixture of monomer, initiator, Lewis acid and solvent without the need of other functionalization effecting compounds such as electron donor type compounds disclosed in the art.
  • the resulting polymer is characterized by the advantages of a high specificity of functionalization combined with a narrower molecular weight distribution.
  • the method of the present invention enables easy control over the desirable molecular weight by adjusting the initial monomer to initiator a concentration ratio without the need of an electron donor.
  • the present invention includes a polymer composition having the formula:
  • R((M)p(Y)) n R is selected from at least one group consisting of H, a hydrocarbyl group, and a hydrocarbyl-substituted silyl group.
  • R can be alkyl, aryl, alkylaryl and arylalkyl.
  • Y is selected from at least one group consisting of an azido, cyano, carbonylamino, thiocarbonylamino, cyanato and thiocyanato; a preferred Y is an azido group.
  • M is at least one repeat unit derived from a cationically polymerizable monomer; useful monomers include straight and branched chain alpha-olefins, isoolefins, alicyclic monoolefins, cycloaliphatic compounds, styrene derivatives, indene and derivatives thereof, and other monoolefins and heterocyclic monomers, p is an integer greater than 1 and preferably sufficient to attain a desired molecular weight, n is an integer of at least 1 , preferably 1 to 10 and most preferably 1 to 2.
  • the polymer can have the plurality of arms ranging from 2 to 10 or more.
  • This type of polymer is considered a "star polymer", but advantageously one in which each arm is substantially equal in length due to the narrow MWD.
  • the nitrogen containing end groups can be reacted to form a desired functional terminal group including amines to prepare new telechelic oligomers.
  • Uses include lubricant dispersants, viscosity improvers, synthetic lubricating oils, and thermoplastic elastomers.
  • the present invention provides a way to obtain, at the same time, complete functionalization of the polymer by a monofunctional pseudohalogen or halogenoid initiator by direct synthesis using living cationic polymerization.
  • the polymer product has a functionality of up to, and preferably, 1.
  • the polymer product has a functionality of up to, and preferably, 2.
  • the polymer has a narrow molecular weight distribution (MWD), or a low polydispersity index, as measured by weight average molecular weight divided by number average molecular weight.
  • the MWD should ideally be 1.0, preferably less than 1.5, preferably from 1.0 up to 1.5, more preferably 1.0 to 1.4, with preferred values typically at 1.1 to 1.4.
  • Preferred polymers produced in accordance with the method of the present invention are telechelic polymers.
  • the functional groups are derived from the initiator with at least one functional group preferably containing nitrogen. In the living polymerization process using an initiator having one functional nitrogen- containing group, the functionality of the polymer is close to the theoretical value of 1 , and typically greater than 0.7. Where the initiator contains more than one pseudohalide function the functionality would be expected to be close to a multiple of the number of functional groups. For example, an initiator containing two pseudohalide functional groups would be expected to have a functionality of greater than 1.4 and preferably close to 2.
  • a living cationic polymerization process comprising polymerization of a monomer in the presence of an initiator and a catalyst, preferably in a solvent under conditions which result in living polymerization.
  • the nitrogen-containing compound employed as initiator in this invention comprises at least one member selected from the group consisting of (i) compounds of the formula:
  • R is hydrogen or a hydrocarbyl group
  • n is a positive integer, preferably an integer of from 1 to 10, more preferably 1 or 2 and Y is -N3, -CN, -NCO, -OC ⁇ N; -SC ⁇ N; or -NCS; and (ii) compounds of the formula:
  • R * comprises a hydrocarbyl-substituted silyl group of the formula:
  • each R is the same or different and is hydrocarbyl.
  • hydrocarbyl R groups are alkyl of from 3 to 100 carbon atoms, preferably 4 to 20 carbon atoms, aryl of from 6 to 20 carbon atoms, preferably from 6 to 15 carbon atoms, alkaryl and aralkyl of from 7 to 100 carbon atoms (e.g., 7 to 20 carbon atoms), and cycloaliphatic of from 3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms.
  • R in Formula (la) generally comprise an alkyl group of from 3 to 12 carbon atoms, preferably from 3 to 20 carbon atoms, such as propyl, butyl, pentyl, octyl, decyl, dodecyl, and the like, and can be a polymeric group.
  • R in Formula (la) comprises a moiety of the formula: R1
  • R " * , R 2 and R 3 are the same or different and are H or hydrocarbyl (e.g., alkyl, aryl, alkaryl, aralkyi, heterocyclic or cycloalkyi) with the proviso that at least two of R 1 , R 2 , and R 3 are hydrocarbyl; most preferably all of R 1 , R 2 and R 3 are hydrocarbyl.
  • exemplary of such secondary and tertiary alkyl groups are isopropyl, tert-butyl, 1-methylpropyl, 1-ethylbutyl, 1 ,2-dimethylbutyl, and the like.
  • R 1 , R 2 or R 3 groups are CH2-, CH30CH2-, -0C2H5 and the like. Further examples of such R - , R 2 or R 3 groups are CH30-, (CH3)2 ⁇ - and the like.
  • the carbonylamino (-NCO) and thiocarbonylamino (-NCS) substituted compounds are isocyanates and isothiocyanates, respectively.
  • hydrocarbyl-substituted nitrogen-containing initiators of Formula (la) can comprise a polymer, having one or more Y-functional groups which can be added by grafting.
  • Useful polymers are, for example, a polyalkene, such as a C2 to C-
  • Useful nitrogen-containing initiators include disubstituted compounds of the formula:
  • Y is as defined above, and Z comprises a
  • R 5 , R 6 , R 7 and R 8 are the same or different and comprise H or hydrocarbyl, e.g., alkyl of from 1 to 100 carbon atoms (e.g., methyl, ethyl, isopropyl, butyl and the like), cycloalkyi of from 3 to 10 carbon atoms (e.g., cyclohexyl, cyclobutyl and the like), aryl of from 6 to 20 carbon atoms (e.g., phenyl, naphthyl and the like), or aralkyi and alkaryl of from 7 to 20 carbon atoms (e.g., tolyl, cresyl, xylyl, benzyl, ethylbenzyl and the like), and R 4 comprises -(CH2) a -, or -Ar-, wherein a is an integer of from 3 to 20, and preferably 3 to 10, and wherein Ar is an arylene group of from
  • a preferred initiator of the present invention is bis(1-azido-1-methylethyl)benzene having the formula:
  • the bis(1-azido-1-methylethyl)benzene can be prepared by reacting dicumyl alcohol with a halogen containing compound to form dicumyl halide.
  • the dicumyl halide is reacted with an azide containing compound to form the bis(1-azido-1- methylethyl)benzene.
  • the halogen-containing compound is preferably a bromide or chloride and more preferably HCI, and the azide containing compound is preferably NaN3.
  • the reactions can be conducted in the presence of suitable solvents under suitable conditions.
  • the dicumyl alcohol can be reacted with HCI in a polar solvent such as methane dichloride under reflux conditions.
  • the dicumyl chloride can be reacted with sodium azide in a solvent under reflux conditions, preferably with a weak Lewis acid catalyst such as ZnCl2- The following preferred reactions have been successfully conducted:
  • the method of the instant invention is illustrated by the production of polyisobutylene functionalized with terminal azido, cyano, carbonylamino or thiocarbonylamino groups.
  • isobutene monomer is provided in a low-boiling, low-freezing alkyl halide solvent.
  • An azido- providing species such as a substituted benzylic type azide such as cumyl azide may be added to the monomer.
  • Functionalization by the azide, cyano, carbonylamino, cyanato, thiocyanato, isothiocyanato, or thiocarbonylamino group can be obtained during the cationic polymerization of the selected monomer (e.g., isobutylene) in the liquid phase.
  • the azide, cyano, carbonylamino, cyanato, thiocyanato, isothiocyanato, or thiocarbonylamino group is introduced in the form of a suitably designed molecule including a release moiety enabling the Y- group to migrate to the electrophilic site of a growing polymer chain.
  • the polymerization in accordance with the process of the present invention is a living cationic polymerization.
  • the degree of polymerization is equal to the concentration of monomer consumed and incorporated in the polymer divided by the initiator concentration. If the rate of initiation is equal to or higher than that of propagation, living polymerizations will yield molecular weight distributions very close to unity; i.e., Mw/Mn is about equal to 1. This latter requirement is not disclosed to be part of the rigorous definition of living polymerization.
  • Initiation and propagation can be separated and controlled individually, for example, by first preparing a quantity of active centers and subsequently adding monomer to this seed or by continuously adding monomer to the active centers.
  • N- containing initiators having Y- groups which are mobile in the presence of Friedel- Crafts catalysts, provide functionalization (during polymerization) of the growing polymer chain ends. This is believed to occur by reaction of the electrophilic site with the complex anion containing the Y- constituent.
  • the introduction of the initiator also herein sometimes termed the "cocatalyst" simultaneously provides an initiation site and a functionalization system enabling the following reaction:
  • R is the release moiety of the cocatalyst
  • N3 is the nitrogen-containing functional group
  • Cat is, for instance, a metal halide catalyst
  • m is the degree of polymerization.
  • the resulting product then theoretically contains functionality at each end. That is, one end of the polymer corresponds to the R group of the nitrogen- containing initiator and the other corresponds to the Y group of the initiator.
  • a difunctional initiator of this invention e.g.,
  • the resulting polymer product will theoretically contain a Y functionality at each end of the polymer, and a R group within the polymer chain.
  • the RY n initiator compound when n > 2, is multifunctional and additional branching of the polymer can occur due to polymer growth at multiple sites on the intiators of this invention.
  • the polyolefin branches are ideally all of the same length. The branches emanate from the R group in a star-like structure.
  • the Y-group e.g., the -N3, azide group
  • the N-containing initiator has sufficient mobility to be transferred to the growing chain end.
  • the Lewis Acid selected to catalyze the polymerization is introduced at a concentration corresponding to greater than three times, preferably four and more, preferably from four to twenty times, the molar equivalents of the Y functional group, i.e., azide or other N-containing group of this invention, charged to the polymerization zone.
  • the preferred N-containing initiators employed in this invention are those in which the Y group is covalently bound to a secondary or tertiary carbon, and those in which the R release moiety is resonance stabilized or otherwise capable of delocalizing charge.
  • the R release moiety is an allylic or benzylic species.
  • the initiator can be monofunctional, di- or multifunctional, and can contain more than one of the above Y functional groups, although it is preferred that di- or multifunctional initiators contain only a single such type of Y group. The functionality of the polymer product is then equal to one, two or more, accordingly.
  • Preferred initiator molecules include 1 -azido-1 -methylethyl benzene, and 2-azido-2-phenyl- propane in which the azide group is at the same time tertiary and of the benzylic type, and bis(1-azido-1-methylethyl)benzene.
  • Hydrazoic acid is also useful as the initiator molecule containing an azide group. In the latter case, the proton of the acid is the fragment on which polymerization is initiated (by cocatalysts), and the functionalization is the result of the termination reaction.
  • Particularly preferred is bis(1-azido-1-methylethyl)benzene, and the compounds derived therefrom.
  • the catalyst can comprise a Friedel-Crafts catalyst or other Lewis Acid cationic polymerization catalyst.
  • the Friedel-Crafts catalyst can comprise an organometallic compound of the formula R 9 n 'MT n " wherein M' is a metal selected from the group consisting of Ti, Al, Sn, Fe and Zn, R 9 is a hydrocarbyl group (preferably a C-
  • organoaluminum halides aluminum halides, boron trifluoride, and titantium halides. Most preferred are organoaluminum chlorides.
  • organometallic halide compounds are known in the art and can be prepared by conventional means, e.g., by the process described in U.S. Patent No. 4,151 ,113 and the references cited therein.
  • Lewis Acid catalysts comprise metal halides (preferably chlorides or bromides), e.g., B and As, such as BCI3, BF3, ASF5, and the mixed halides thereof such as BCIF2, and the various "sesqui” derivatives of elements of Group IIIA (Group 13 in the new notation) of the Periodic Table of the Elements, such as 62(0 ⁇ 5)3 ⁇ 3803)3, Al2(C2H5)3Cl3, and the like.
  • Preferred catalysts are amongst the relatively "weak" Lewis acids such as diethylaluminum chloride, ethylaluminum dichloride.
  • Lewis acids such as boron trichloride or titanium tetrachloride, depending on the solvent and monomer used, are useful although not preferred since control of molecular weight and MWD is not as good as with the "weak" Lewis acids. When the Lewis acids are too weak, no polymerization is observed.
  • Most preferred Friedel-Crafts Lewis acid catalysts are organoaluminum halides. Although insoluble catalysts may be used, the catalyst is preferably soluble in the reaction medium, and the exact concentration of the catalyst depends on the concentration of the molecule containing the Y group.
  • the Lewis acid catalyst and N-containing initiator are charged to the polymerization zone in moles of Lewis Acid catalyst to moles of initiator in a ratio of greater than 3.1 to 1 , preferably from 4:1 to 30:1 , and more preferably from 5:1 to 20:1 , a particularly useful range of greater than 6: 1 and specifically greater than 6.1 : 1.
  • Molecular weight of the product may be controlled by controlling the ratio of the moles of monomer M to moles of initiator I; molecular weight increases as this latter ratio increases.
  • Suitable solvents include, but are not limited to, low-boiling alkyl halides, whether they are mono- or polyhalides, the requirement being a reasonably low freezing point to be used at the preferred polymerization temperature.
  • Illustrative diluents or solvents useful in cationic polymerization include alkanes (generally C2 to C10 alkanes, including normal alkanes such as propane, n-butane, n-pentane, n- hexane, n-heptane, and branched alkanes including isobutane, isopentane, isohexane, 3-methylpentane, and the like), alkenes and alkenyl halides (such as vinyl chloride), carbon disulfide, chloroform, ethylchloride, N-butyl chloride, methylene chloride, methylchloride, 1 ,2-dichloroethane, carbon tetrachlor
  • Any cationically polymerizable monomers may be used, including straight and branched chain alpha olefins, isoolefins, alicyclic monoolefins, cycloaliphatic compounds, styrene derivatives, indene and derivatives, and other monoolefins and heterocyclic cationically polymerizable monomers identified in the text by J.P. Kennedy "Cationic Polymerization of Olefins: A Critical Inventory” pages 39 to 53 (John Wiley & Sons, 1975). Vinyl ethers can also be used.
  • Particularly valuable polymers can be prepared from isoolefins of from 4 to 20 carbon atoms or mixtures thereof to produce homopolymers and copolymers.
  • unsaturated hydrocarbons include, but are not restricted to, isobutylene, 2-methylbutene, 3-methylbutene-1 , 4-methylpentene-1 , and beta-pinene.
  • Other cationically polymerizable monomers which may be employed include heterocyclic monomers such as oxazolines and others known to add onto polarized covalent bonds.
  • feedstocks to the polymerization zone comprise pure isobutylene and mixed C4 hydrocarbon feedstocks containing isobutylene, such as a C4 cut resulting from the thermal or catalytic cracking operation of, for example, naphtha.
  • suitable isobutylene feedstocks will typically contain at least 10%, and up to 100% isobutylene, by weight, based on the weight of the feed.
  • feedstocks containing isobutylene may also contain other non-C4 polymerizable olefin monomers in minor amounts, e.g., typically less than about 25%, preferably less than about 10%, and most preferably less than 5%, such as propadiene, propylene and C5 olefins.
  • polyisobutene as employed herein is intended to include not only homopolymers of isobutylene but also copolymers of isobutylene and one or more other C4 polymerizable monomers of conventional C4 cuts as well as non-C4 ethylenically unsaturated olefin monomers containing typically from 3 to 6, and preferably from 3 to 5 carbon atoms, provided such copolymers contain typically at least 50%, preferably at least 65%, and most preferably at least 80% isobutylene units, by weight, based on the polymer number average molecular weight (Mn).
  • Mn polymer number average molecular weight
  • the polymerization medium is substantially free of substances which are capable of initiating the catalysts other than the selected N-containing initiator (or mixtures of initiators) of this invention. Therefore, the polymerization medium preferably should be substantially free of added conventionally employed cationic polymerization initiators or promoters (i.e., cocatalysts) such as water, alcohols, carboxylic acids and acid anhydrides, HF, ethers or mixtures thereof.
  • the alcohols which should be excluded are straight or branched chain, aliphatic, aromatic, or mixed aliphatic/aromatic alcohols containing from 1 to 30 carbon atoms.
  • the carboxylic acid, acid anhydride and/or ether promoters to be excluded are halogen substituted or unsubstituted, straight or branched chain, aliphatic, aromatic or mixed aliphatic/aromatic acids and ether containing from 1 to 30 carbon atoms.
  • the polymerization reaction medium preferably contains less than 20 weight ppm of water, and less than 5 weight ppm of mercaptans, all of which can function as poisons to Lewis Acid catalysts.
  • the olefin feed can be treated to achieve the above desired levels by conventional means, e.g., by use of mole sieves and caustic washing to remove mercaptans and water to the above, and dienes (if desired).
  • the polymerization reaction may be conducted batchwise or in semicontinuous or continuous operation in which continuous streams of ingredients are delivered to the reactor, and an overflow of a slurry or solution of polymer is taken out for the recovery of the polymer therefrom.
  • the preferred mode of reaction is on a continuous basis using a continuous flow stirred reactor wherein feed is continuously introduced in a controlled manner into the reactor and product continuously removed in a controlled manner from the reactor.
  • the amount of Lewis Acid catalyst employed in the process of the present invention can be controlled in conjunction with the reaction temperature to achieve the target number average molecular weight of polymer but is also sought to be minimized to reduce undesired isomerizations believed to be induced thereby.
  • the catalyst amount also affects the conversion of the olefin monomer and yield of polymer, with higher amounts of Lewis Acid catalyst typically achieving higher conversions and yields. Strong Lewis Acid catalyst can lead to isomerizations which reduce the functionality of the polymer, and can produce chain transfer. Thus, in the process of the present invention, a weaker or milder Lewis acid is preferred.
  • the catalyst should be employed in sufficient amount to enable the reaction to be a "living" cationic polymerization.
  • the preferred catalyst concentration corresponds to about the quantitative formation of complex between the catalyst and the nitrogen- containing compound. More specifically, the catalyst employed at a ratio of moles of Lewis Acid to equivalents of nitrogen-containing functional groups of more than 3.1 :1 , preferably more than 4:1 , more preferably more than 6:1 , with a preferred range of from 3.1 :1 to 30:1 , more preferably 4:1 to 20:1 and most preferably 6:1 to 10:1.
  • the Lewis acid to initiator molar ratios is preferably from 3:1 to 5:1.
  • the polymerization reaction is conducted in the liquid phase to induce linear or chain type polymerization in contradistinction to ring or branch formation.
  • a feed which is gaseous under ambient conditions, it is preferred to control the reaction pressure and/or dissolve the feed in an inert solvent or liquid diluent, in order to maintain the feed in the liquid phase.
  • Typical C4 cuts comprising the feed are liquid under pressure and do not need a solvent or diluent.
  • the selected Lewis Acid catalyst is normally a gas (e.g., BF3, and the like) the catalyst is typically introduced into the reactor as gas which is partially or completely dissolved in a pressurized liquid in the reactor.
  • Polymerization pressures can range typically from 25 to 500, and preferably from 100 to 300, kpa.
  • the N-containing initiator can be introduced to the monomer feed, or to the reaction mixture, in liquid form preferably separately from the Lewis Acid catalyst.
  • the monomer is not contacted with the Lewis Acid catalyst in the absence of the N-containing initiator of this invention.
  • the temperature at which the polymerizations are carried out is important, since temperatures which are too high tend to decrease the functionalization degree.
  • the usual polymerization temperature range is between 100°C and +10°C.
  • the polymerizations are performed at a temperature below -10°C, preferably below -20°C, and preferably between -80°C and -20°C, e.g. at a temperature of -50 C C.
  • the liquid phase reaction mixture temperature is controlled by conventional means.
  • the particular reaction temperature is selected to achieve the target living polymerization behavior, and preferably is not allowed to vary more than + or -5 ⁇ C from the selected value, while the catalyst and/or promoter feed rate is varied to achieve the desired Mn to compensate for variations in monomer distribution in the feed composition.
  • Average polymerization times, in minutes can vary from 10 to 120, preferably from 15 to 45 (e.g., 20 to 30), and most- preferably from 15 to 25.
  • the materials used to quench the reaction are conventional and include the same materials conventionally used as cationic polymerization promoters (e.g., moisture, alcohol) with the exception that excess quantities are employed in amounts sufficient to deactivate the catalyst.
  • any amount of quenching medium effective to deactivate the catalyst may be employed, it is contemplated that such effective amount be sufficient to achieve a molar ratio of quench medium to Lewis Acid catalyst of typically from 1 :1 to 100:1 , preferably from 3:1 to 50:1 , and most preferably from 10:1 to 30:1.
  • Quench is conducted by introducing the quench medium into the polymer product.
  • the polymer product is maintained under pressure during the quench sufficient to avoid vaporization of any gaseous Lewis Acid catalyst (if one is employed) and other components of the mixture.
  • the temperature of the quenching medium is not critical and, e.g., can comprise room temperature or lower.
  • quench can be performed in the reactor or preferably on the product after it is withdrawn from the reactor. In a continuous system, the quench will typically be performed after product exits the reactor.
  • the polymerization product is typically subjected to conventional finishing steps which include a caustic/H2 ⁇ wash to extract catalyst residue, a hydrocarbon/aqueous phase separation step wherein deactivated and extracted Lewis Acid catalyst is isolated in the aqueous phase, and a water washing step to remove residual amounts of neutralized catalyst.
  • the polymer is then typically stripped in a debutanizer to remove unreacted volatile monomers, followed by a further stripping procedure to remove light end polymer (e.g., C24 carbon polymer).
  • the stripped polymer is then typically dried by N2.
  • the present invention includes a polymer composition having the formula:
  • R is selected from at least one group consisting of H, a hydrocarbyl group, and a hydrocarbyl-substituted silyl group.
  • R can be alkyl, aryl, alkylaryl and arylalkyl.
  • Y is selected from at least one group consisting of an azido, cyano, carbonylamino, thiocarbonylamino, cyanato and thiocyanato.
  • a preferred Y is an azido group.
  • M is at least one repeat unit derived from a cationically polymerizable monomer.
  • Useful monomers include straight and branched chain alpha olefins, isoolefins, alicyclic monoolefins, cycloaliphatic compounds, styrene derivatives, indene and derivatives thereof, and other monoolefins and heterocyclic monomers, p is an integer greater than 1 and preferably sufficient to attain a desired molecular weight, n is an integer of at least 1 , preferably 1 to 10 and most preferably 1 to 2.
  • the novel polymers of this invention comprise terminally substituted polymers derived from any of the above-discussed cationically polymerizable monomers.
  • the polymers will preferably contain at least 5 monomer units (M) per polymer chain, and will more usually be characterized by number average molecular weights of at least 350 or less and up to 15,000,000 or more with a useful range of from 350 to 15,000,000.
  • the molecular weight range can be determined for particular polymers.
  • preferred polymers generally range from 500 to 2,000,000 with derivatives of functionalized polymer used as lubricant additives generally up to 100,000 and with specific ranges of from 500 to 20,000 for use as dispersants and 20,000 to 100,000 for use as viscosity improvers.
  • the polymerization of the present invention can be conducted in a manner and under conditions to attain various molecular weight polymers.
  • Low molecular weight polymers are considered to be polymers having a number average molecular weight of less than 20,000, preferably from 500 to 10,000, (e.g. from 2,000 to 8,000) and most preferably from 1 ,500 to 5,000. Molecular weights in this range are conveniently measured by vapor phase osmometry. Low molecular weight polymers are useful in forming dispersants for lubricant additives.
  • Medium molecular weight materials having a number average molecular weight range of from 20,000 to 200,000, preferably 25,000 to 100,000; and more preferably from 25,000 to 80,000 are useful for viscosity improvers for lubricating oil compositions, adhesive coatings, tackifiers and sealants.
  • the medium number average molecular weights can be determined by membrane osmometry.
  • the higher molecular weight materials have a number average molecular weight range of greater than 200,000 to 15,000,000, specifically 300,000 to 10,000,000 and more specifically 500,000 to 2,000,000. These polymers are useful in polymeric compositions and blends including elastomeric compositions.
  • Mw/Mn also referred to as molecular weight distribution, (MWD) are not critical. However, a typical maximum Mw/Mn value of 1.5 is preferred with typical ranges of 1.1 up to 1.4. The ideal MWD is 1.0.
  • the polyalkenes may include aromatic groups (especially phenyl groups and lower alkyl- and/or lower alkoxy-substituted phenyl groups such as para-(tert- butyl)phenyl and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cycloaliphatic substituted-polymerizable acrylic olefins, the polyalkenes usually will be free from such groups.
  • aromatic and cycloaliphatic groups can be present, the olefin monomers from which the polyalkenes are prepared can contain aromatic and cycloaliphatic groups.
  • polyalkenes include polypropylen ⁇ s, polybutenes, ethylene-propylene copolymers, ethylene-tert-butene, styrene-isobutene copolymers, isobutene- (paramethyl)styrene copolymers, copolymers of octene-1 , copolymers of 3,3- dimethyl-pentene-1 with hexene-1 , and copolymers of isobutene and styrene.
  • poly(isobutene)s obtained by polymerization of C4 refinery stream having a butene content of about 35 to about 75% by weight and an isobutene content of about 30 to about 60% by weight. These polybutenes contain predominantly (greater than about 80% of the total repeating units) of isobutene repeating units of the configuration:
  • poly-n-butenes made by the process of the present invention.
  • a preferred source of n-butenes is petroleum feedstreams such as Raffinate II. These feedstocks are disclosed in the art such as in U.S. Patent No. 4,952,739. These C4 feedstreams preferably is substantially free of sulfur contaminants (e.g., mercaptans) e.g. ⁇ 20 wppm H2S and 5 wppm S and is preferably substantially anhydrous, that is, it contains less than 300 wppm water, based on the C4 monomers in the feedstream as well as less than 100 ppm of methanol (which may be present if the feedstream is derived from Raffinate I used to make MTBE).
  • sulfur contaminants e.g., mercaptans
  • methanol which may be present if the feedstream is derived from Raffinate I used to make MTBE.
  • the C4 products other than butenes functions as diluent or solvent in the reaction mixture and are a non-critical aspect of this invention.
  • the process of the present invention has enabled a new class of polymers and copolymers to be made from Raffinate II feedstock rendering a substantially low value feedstream as a valuable new raw material.
  • the living polymers of the present invention will comprise terminal substituent Y groups on one end, and a terminal R group on the other end when the nitrogen- containing initiator comprises a R-Y or R * -Y compound.
  • R and R * are discussed above with regard to formulae (la, lb and lc).
  • the resulting polymers have the following structures: R-[polyolefin]-Y; and R*-[polyolefin]-Y.
  • a poly-functional initiator such as the bifunctional initiator of Formula III above, the polymers will comprise terminal Y-groups on each end of the polymer and a R group within the polymer chain, e.g., substantially at the center of the polymer chain.
  • the poly-substituted polymers of this invention have the following structure: Y-[polyolefin]- R-[polyolefin]-Y.
  • the nitrogen functionalized polymeric materials of the present invention are useful by incorporation and dissolution into an oleaginous material such as fuels and lubricating oils.
  • an oleaginous material such as fuels and lubricating oils.
  • a concentration of the polymers in the fuel will be in the range of typically from 0.001 to 0.5, and preferably 0.005 to 0.15 wt. %, based on the total weight of the composition.
  • a concentration of the polymers in the lubricating oil is in the range of from 0.01 to 15 wt.
  • the polymers may be employed in lubricating oil compositions which employ a base oil in which the polymers are dissolved or dispersed. Such base oils may be natural or synthetic.
  • Base oils suitable for use in preparing the lubricating oil compositions of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like.
  • the polymers of this invention are also useful as polymerization additives, e.g. as cross-linking agents and polymerization comonomers, and the polymers can be employed to prepare molded or extruded articles such as films.
  • the polymers of this invention are also useful components for the synthesis of block copolymers and star copolymers. These polymer materials can be used as compatibilizer or as thermoplastic elastomers.
  • the polymers of the present invention include functional reaction products of the above-recited polymers containing nitrogen groups, particularly -N3, -NCO, -OCN, -SCN, -CN and -NCS groups.
  • Such functional reaction products are the reaction product of the nitrogen functional groups of the nitrogen-containing polymer with a functional reactant compound. This is illustrated by the reaction of -N3 (azido) containing polymer derived from formula IV, where -Y is -N3, i.e., (R(M)p(-N3)) n where R, M, p and n are as defined above. For illustration purposes n equals one.
  • the azido R(M)p-N3 can be reacted to form functional reaction product polymers containing the following functional groups:
  • R 20. -C C- -R21 ;
  • R(M) p N NR(M) p ; (11 )
  • R 20 to R 33 are the same or different and can be selected from hydrogen, a hydrocarbyl group and a substituted hydrocarbyl group.
  • R 20 to R 33 can be -H, and alkyl, aryl, alkylaryl, or aryialkyi group, X is a halide, preferably a chloride group.
  • Useful R 20 to R 33 alkyl groups include C-
  • Reactions of azides to prepare the above functional reactant product polymers include those of types known in the art. Typically, they can be conducted under mild conditions in a suitable solvent.
  • a useful solvent is tetrahydrofuran (THF) at 0°C - 100°C and 1 atmosphere.
  • THF tetrahydrofuran
  • a useful reaction of the present invention to form a polymer triazoles useful as lubricant additives is:
  • a useful reaction of the present invention is the reaction of an anhydride, preferably maleic anhydride with a triazole.
  • R 24 and R 25 are an -H group.
  • formula (3) being R(M)pNH2; this amine can be used as an additive for lubricants.
  • the conversion of azides to nitrites is disclosed in the Bull. Chem. Soc. of Japan, 49 p. 506 (1976) and the J. Org. Chem., Vol. 44, No. 16, p. 2951 (1976); applied to decomposition of an azide of the present invention:
  • the R(M) p C ⁇ N can be further reacted to form an amine, i.e., with H2 to form R(M) p CNH2.
  • the catalyst can be Pd or those referred to in the above publications.
  • the amine is useful as an additive for lubricating oils.
  • An alternative and preferred method of producing amine derivatized polymer from azido functionalized polymer is by reducing the azido group to form an amine group. The reduction is preferably accomplished by reducing the azido functionalized polymer in the presence of a reducing catalyst to form the amine.
  • Useful reducing catalysts include L.AIH4, CaH2 and the like, with UAIH4 most preferred.
  • the reaction is preferably conducted in a suitable solvent for the polymer and the catalyst, preferably a polar solvent such a tetrahydrofuran (THF).
  • a suitable solvent for the polymer and the catalyst preferably a polar solvent such as a tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the reaction can be conducted at room temperature or under reflux conditions.
  • hydroxyl type bases and solvents for the base and polymer can be used, with KOH preferred.
  • the polymer containing hydroxyl group can be reacted with acids, i.e. carboxylic acids to form esters which are useful as additives for lubricating oil compositions.
  • Isocyanates can be formed by the reaction of azides and CO as disclosed in J. Am. Chem. soc. 90, 3295 (1968); the reaction can be applied herein as follows:
  • the R(M)pNCO can be reacted with an amine to form
  • R 28 is -H, and at least one of R 27 and R 28 is -H.
  • Nitrogens can be formed from azides by decomposing by heat or light.
  • R(M) p N + R 29 R 3 0-C CR 3 1 R 32 > R 29 R 3 0C-CR 1 R 32 (8)
  • the nitrenes of formula (9) can rearrange to form imines. This type of chemistry is reviewed in Moriarty et al., The Direct and Photosensitized Decomposition of Alkyl Azides. Tetrahedron, 26, 1379 (1970) and J. Am. Chem. Soc. 93, 1537 (1971 ):
  • the functionalized reactant product polymer can be used as a dispersant if the functional group contains the requisite polar group. However, derivatives of various of the functionalized polymers can be formed. These derivatized polymers have the requisite properties for uses such as dispersants and viscosity modifiers.
  • Reactant functional groups of the functionalized polymer can be reacted with derivative compounds to form derivatized polymers.
  • the derivative compound comprises at least one reactive derivative group.
  • the derivatized compound preferably contains at least one additional group which makes the derivatized group polar or reactive.
  • Such derivatized polymers can contain amine groups, carboxyl groups or groups derived from reactive metal or reactive metal compounds.
  • Various of the functional reactant product polymers can be further chemically modified to improve the polymer properties or impact desirable properties not otherwise present.
  • a chemical moiety can be directly or indirectly reacted at various of the nitrogen- containing functional reactant groups included in formulae (1 ) to (14).
  • Such modified, derivatized compounds include the reaction product of formula (2), particularly wherein the anhydride is maleic anhydride, with derivative compounds, and formula (6), isocyanato, with compounds containing carboxyl groups.
  • the functionalized polymer having the amine groups of formulae (3) and (14), and alcohol groups of formula (5) can be used directly, i.e. as dispersants or V.I. improvers for lubricating oil compositions or further derivatized with carboxyl-containing derivative compounds.
  • the derivatized polymer can include the reaction product of the above recited functionalized polymer (i.e.
  • the derivatized polymers are useful as lubricant dispersants which maintain oil insolubles (resulting from oxidation during use) in suspension in the fluid, thus preventing sludge flocculation and precipitation.
  • the compounds useful as dispersants generally are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group generally contains up to 10 wt. %, and typically from 0.1 to 5 wt.
  • solubilizing chains are generally higher in molecular weight than those employed with the metallic based dispersants, but in some instances they may be quite similar.
  • Various types of dispersants can be made using the derivatized polymer of the present invention and are suitable for use in the lubricant compositions. The following are illustrative:
  • Reaction products of carboxylic acid or anhydride functionalized reactant polymer i.e. formula (2) of the present invention (or derivatives thereof) derivatized with nitrogen-containing compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials.
  • reaction products or isocyanato derivatized polymer (formula (6)) to form urea, and alcohols to form urethanes.
  • Such reactions are typically conducted by mixing the component with or without solvents (depending on molecular weight) at ambient conditions.
  • the derivatized living polymer can also be used to make ash and ashless type detergents.
  • the living polymer for use as a detergent is an alkyl polymer having a number average molecular weight of from 300 to 900.
  • the ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with alkyl derivatized polymer sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the derivatized olefin polymer of the present invention with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
  • salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
  • basic salt is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the derivatized polymer, such as with maleic anhydride (or acid) and methods for preparing such salts are well known in the art.
  • Preferred ash-producing detergents which can be derived from the functionalized reactant polymer of the present invention include the metal salts of sulfonic acid derivatives, preferably wherein the polymer is an alkyl compound, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, alkyl naphthenates and other oil soluble mono- and dicarboxylic acids.
  • Highly basic (viz, overbased) metal salts such as highly basic alkaline earth metal alkyl sulfonates (especially Ca and Mg salts) are frequently used as detergents and their production is well known in the art.
  • Useful amine compounds for derivatizing polymers having functional groups or reactive derivative groups comprise at least one amine and can comprise one or more additional amines or other reactive or polar groups.
  • the reactant functional group is a carboxylic acid, ester or derivative thereof, or an isocyanato, it reacts with the amine to form an amide.
  • the functional group is a halide the amine reacts to displace the halide.
  • the reaction functional group is an isocyanate it reacts with an amine to form a urea, and an alcohol to form a urethane.
  • Amine compounds useful as nucleophilic reactants for reaction with the functionalized polymer of the present invention include those disclosed in U.S. Patent Nos.
  • Preferred amine compounds include mono- and (preferably) polyamines, of 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atoms of 1 to 12, preferably 3 to 12, and most preferably 3 to 9 nitrogen atoms in the molecule.
  • These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g., hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups, are particularly useful.
  • amine compounds include: alicydic diamines such as 1 ,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines. Commercial mixtures of amine compounds may advantageously be used. Low cost poly(ethyleneamine) compounds averaging 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", “Polyamine 400", “Dow Polyamine E-100", etc. Useful amines also include polyoxyalkylene polyamines. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc.
  • a particularly useful class of amines are the polyamido and related amines disclosed in U.S. Patent Nos. 4,857,217; 4,963,275 and 4,956,107.
  • Preferred compounds for reaction with the polyamines in accordance with this invention are lower alkyl esters of acrylic and (lower alkyl) substituted acrylic acid.
  • the amine compound can be reacted with the functionalized polymer by heating an oil solution containing 5 to 95 wt. % of functionalized polymer to 100°C to 200°C, preferably 125°C to 175°C, generally for 1 to 10, e.g. 2 to 6 hours until the desired amount of water is removed.
  • the heating is preferably carried out to favor formation of imides or mixtures of imides and amides, rather than amides and salts.
  • Reaction ratios of dicarboxylic acid material to equivalents of amine as well as the other nucleophilic reactants described herein can vary considerably, depending upon the reactants and type of bonds formed. Generally from 0.1 to 1.0, preferably 0.2 to 0.6, e.g.
  • moles of functionalized groups present in the functionalized polymer is used, per equivalent of nucleophilic reactant, e.g. amine.
  • nucleophilic reactant e.g. amine.
  • 0.8 mole of a pentamine (having two primary amino groups and 5 equivalents of nitrogen per molecule) is preferably used to convert polymer functionalized with succinic anhydride into a mixture of amides and imides, i.e. preferably the pentamine is used in an amount sufficient to provide 0.8 mole (that is (2) (1.6)/[0.8 x 5] mole) of carboxy functional groups (0.4 moles of succinic groups) per nitrogen equivalent of the amine.
  • Tris(hydroxymethyl) amino methane can be reacted with the aforesaid functionalized polymers to form amides, imides or ester type additives as taught by U.K. 984,409, or to form oxazoline compounds and borated oxazoline compounds as described, for example, in U.S. Patent Nos. 4, 102,798; 4, 116,876 and 4, 113,639.
  • the polymers of the present invention functionalized with acid groups can be reacted with alcohols to form esters.
  • the alcohols may be aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols.
  • the polymer containing isocyanato functionality reacted with alcohols to form urethanes. Phenol and alkylated phenols having up to three alkyl substituents are preferred.
  • the alcohols from which the esters may be derived preferably contain up to 40 aliphatic carbon atoms.
  • the polyhydric alcohols preferably contain from 2 to 10 hydroxy radicals.
  • a useful class of polyhydric alcohols are those having at least three hydroxy radicals, some of which have been esterified with a monocarboxylic acid having from 8 to 30 carbon atoms.
  • the esters and urethanes may also be derived from unsaturated alcohols.
  • Still another class of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and amino-alcohols.
  • the ether- alcohols having up to 150 oxyalkylene radicals in which the alkylene radical contains from 1 to 8 carbon atoms are preferred.
  • the esters may be diesters or acidic esters as well as mixtures. The esters may be prepared by methods known in the art.
  • the esterification is usually carried out at a temperature above 100 ⁇ C, preferably between 150°C and 300°C.
  • the water formed as a by-product is removed by distillation as the esterification proceeds.
  • a solvent may be used in the esterification to facilitate mixing, temperature control, and removal of water from the reaction mixture.
  • Useful solvents include xylene, toluene, diphenyl ether, chlorobenzene, and mineral oil. Esters obtained by the reaction of stoichiometric amounts of the acid reactant and hydroxy reactant are preferred.
  • Ester derivatives likewise may be obtained by the reaction of acid or anhydride functionalized polymer with epoxide or a mixture of an epoxide and water.
  • acid functionalized polymer a polymer functionalized with lactone acid or a acid halide may be used in the processes above for preparing the ester derivatives of this invention.
  • acid halides may be acid dibromides, acid dichlohdes, acid monochlorides, and acid monobromides.
  • esters include acidic esters and neutral esters.
  • Acidic esters are those in which less than all of the functional groups in the functionalized polymer are esterified, and hence possess at least one free functional group.
  • the functionalized, e.g. acid functionalized, polymers of this invention are reacted with the alcohols according to conventional esterification techniques. This normally involves heating the functionalized polymer with the alcohol, optionally in the presence of a normally liquid, substantially inert, organic liquid solvent/diluent and/or in the presence of esterification catalyst. Temperatures of at least 100°C up to the decomposition point are used. This temperature is usually within the range of 100°C up to 300°C with temperatures of 140°C to 250°C often being employed.
  • Derivatized polymers can be prepared from reactive metal/metal compounds.
  • Useful reactive metals or reactive metal compounds are those which will form metal salts or metal-containing complexes with the functionalized polymer.
  • Metal complexes are typically achieved by reacting the carboxyl functionalized polymers with amines and/or alcohols as discussed above, and also with complex forming reactants either during or subsequent to amination.
  • Reactive metal compounds for 0 use in the formation of complexes with the reaction products of functionalized polymer and amines include those disclosed in U.S. Patent No. 3,306,908, Re. 26,433, U.S. Patent No. 3,271,310 and Canadian Patent No. 956,397.
  • Another aspect of this invention involves the post treatment of derivatized polymers.
  • the processes for post-treating the functionalized or derivatized polymers useful as dispersant materials are analogous to the post-treating processes used with respect to conventional dispersants and multi-functional viscosity index improvers 5 useful as dispersants of the prior art. Accordingly, the same reaction conditions, ratio of reactants and the like can be used. Reference is made to U.S. Patent No. 5,017,199.
  • Derivatized polymers can be post-treated with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon- substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus 0 compounds or the like.
  • the amine derivatized polymers can be treated with a boron compound selected from the class consisting of boron oxide, boron halides, boron acids and esters of boron acids in an amount to provide from 0.1 atomic proportion of boron for each mole of said nitrogen composition to 20 atomic proportions of boron for each atomic proportion of nitrogen of said nitrogen 5 composition.
  • Borated derivatized polymers useful as dispersants can contain from 0.05 to 2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron based on the total weight of said borated nitrogen-containing dispersant compound. Treating is readily carried out by adding from 0.05 to 4, e.g. 1 to 3 wt. % (based on the weight of said nitrogen compound) of said boron compound, preferably boric acid which is most usually added as a slurry to said nitrogen compound and heating with stirring at from 135°C to 190°C, e.g. 140°C to 170°C, for from 1 to 5 hours followed by nitrogen stripping at said temperature ranges.
  • the derivatized polymers of the present invention can also be treated with polymerizable lactones (such as epsilon-caprolactone) to form dispersant adducts having the moiety -[C(0)(C2) z O] m H, wherein z is a number of from 4 to 8 (e.g., 5 to 7) and m has an average value of from 0 to 100 (e.g., 0.2 to 20).
  • polymerizable lactones such as epsilon-caprolactone
  • the functionalized or derivatized polymers of this invention can be post-treated with a C5 to Cg lactone, e.g., epsilon-caprolactone, by heating a mixture of the polymers and lactone in a reaction vessel in the absence of a solvent at a temperature of 50°C to 200°C, more preferably from 75°C to 180°C, and most preferably from 90°C to 160°C, for a sufficient period of time to effect reaction.
  • a solvent for the lactone, dispersant material and/or the resulting adduct may be employed to control viscosity and/or the reaction rates.
  • Catalysts useful in the promotion of the lactone-dispersant material reactions are selected from the group consisting of stannous octanoate, stannous hexanoate, tetrabutyl titanate, a variety of organic-based acid catalysts and amine catalysts, as described on page 266, and forward, in a book chapter authored by R. D. Lundberg and E. F. Cox, entitled “Kinetics and Mechanisms of Polymerization: Ring Opening Polymerization", edited by Frisch and Reegen, published by Marcel Dekker in 1969, wherein stannous octanoate is an especially preferred catalyst.
  • the above discussions relate to a variety of materials including the polymer per se, the functionalized polymer, the derivatized polymer, and post-treated derivatized polymer.
  • the polymer per se has a variety of utilities depending on its molecular weight including synthetic base oil (for lower molecular weights), adhesive coatings (for intermediate molecular weights), and as elastomeric compositions (for high molecular weights), e.g. films, extrudates, composites, and the like.
  • the functionalized polymer in addition to acting as intermediates for dispersant and in multifunctional viscosity improvers (MFVI) manufacture, can be used as molding release agents, molding agents, metal working lubricants, paint thickeners, and the like.
  • additives The primary utility for all the above described materials, from polymer all the way through post-treated derivatized polymer is as an additive for oleaginous compositions.
  • additives the above-mentioned materials are collectively and individually referred to herein as "additives" when use in the context of an oleaginous composition containing such "additives”.
  • the additives of the present invention can be used by incorporation and dissolution into an oleaginous material such as fuels and lubricating oils.
  • a concentration of the additives in the fuel in the range of typically from 0.001 to 0.5, and preferably 0.005 to 0.15 wt. %, based on the total weight of the composition, will usually be employed.
  • Useful compositions and additives are disclosed in U.S. Patent No. 5,102,566.
  • the additives of the present invention find their primary utility in lubricating oil compositions which employ a base oil in which the additives are dissolved or dispersed therein.
  • base oils may be natural or synthetic.
  • Base oils suitable for use in preparing the lubricating oil compositions of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like.
  • Advantageous results are also achieved by employing the additive mixtures of the present invention in base oils conventionally employed in and/or adapted for use as power transmitting fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like.
  • Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incorporation therein of the additives of the present invention.
  • These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations. Among these types of additives are included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, friction modifiers, etc.
  • the additives of this invention can be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then the concentrate is blended with a lubricating oil basestock to obtain the final formulation.
  • Such dispersant concentrates will typically contain (on an active ingredient (A.
  • the lubricating oil basestock for the additive typically is adapted to perform a selected function by the incorporation of additional additives therein to form lubricating oil compositions (i.e., formulations).
  • these concentrates may be diluted with 3 to 100, e.g., 5 to 40 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g.
  • crankcase motor oils The purpose of concentrates, of course, is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.
  • the additive of the presnt invention and formulations containing them would usually be employed in the form of a 40 to 50 wt. % concentrate, for example, in a lubricating oil fraction.
  • the additives of the present invention will be generally used in admixture with a lube oil basestock, comprising an oil of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
  • Useful oils are described in U.S. Patent Nos. 5,017,299 and 5,084,197. -
  • the additives of the present invention may be mixed with other types of additives selected to perform at least one desired function. Typical of such functions are detergent/inhibitor, viscosity modification, wear inhibitor, oxidation inhibitor, corrosion inhibitor, friction modifier, foam inhibitor, rust inhibitor, demulsifier, lube oil flow improvers, and seal swell control. As is well known in the art, some of the additives can provide multiple effects e.g., a dispersant oxidation inhibitor. Compositions, when containing these additives, typically are blended into the base oil in amounts which are effective to provide their normal attendant function. Representative effective amounts of such additives are illustrated as follows:
  • additive concentrates comprising concentrated solutions or dispersions of the subject additives of this invention (in concentrate amounts hereinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the concentrate or additive- package will typically be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant.
  • the subject additives of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive-packages containing active ingredients in collective amounts of typically from 2.5 to 90%, and preferably from 15 to 75%, and most preferably from 25 to 60% by weight additives in the appropriate proportions with the remainder being base oil.
  • the final formulations may employ typically 10 wt. % of the additive-package with the remainder being base oil. (All weight percents expressed herein, unless otherwise indicated, are based on active ingredient (A.I.) content of the additive, and/or upon the total weight of any additive-package, or formulation which will be the sum of the A.I. weight of each additive plus the weight of total oil or diluent).
  • Example 1 (Comparative) In a three necked round bottom 250 ml flask, equipped with a magnetic stirrer,
  • Teflon (PTFE) taps and rubber cap for the introduction of some of the reactants by a syringe, connected to a vacuum line, 0.73 g of 1-azido-1-methylethyl benzene were introduced followed by 100 ml of methylene dichloride. This solvent was previously dried by storage under vacuum after purification over phosphorous pentoxide. The reactor was pumped off and 12 ml of isobutylene, previously dried under calcium hydride, were condensed inside the flask.
  • the reactor was then cooled down to - 50°C, and 11 ml of a one molar solution of diethylaluminum chloride (DEAC) in heptane were introduced by a syringe through a rubber cap.
  • the system was allowed to stand for 50 minutes and quenching was carried out by the introduction of 10 ml of methanol.
  • the mixture was then treated with 100 ml of heptane filter to eliminate catalyst residues and concentrated.
  • Polyisobutylene polymer (PIB) was collected by precipitation in acetone, filtered and dried under secondary vacuum to constant weight. The yield (7.2 g) was considered as complete and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC).
  • Example 2 This example is provided for comparison with Examples 2 - 5.
  • the initiator in Example 1 was 1 -azido-1 -methylethyl benzene, while that in Examples 2 - 5 was bis(1-azido-1-methylethyl)benzene.
  • Example 1 The technology of Example 1 was followed with the exceptions summarized in the following table:
  • the reactor was then flushed with dry nitrogen and 0.053 g of bis-1 ,4-(1-azido-1-methylethyl)benzene were introduced, followed by approximately 97 ml of methylene dichloride which solvent was previously dried by distillation over phosphorous pentoxide and stored under vacuum before use.
  • the reactor was rapidly pumped off and 1.0 ml of isobutylene, previously dried under calcium hydride, was condensed inside the flask.
  • the reactor was cooled to -50°C, and 1.7 ml of DEAC (1M in heptane) were introduced by a syringe through a rubber cap.
  • the isobutene concentration was 0.11 mole/1
  • the concentration of initiator was 2.2 x 10" 3 mole/1
  • the DEAC was 1.7 x 10 "2 mole/1.
  • the molar ratio Lewis acid/azide group was 3.86.
  • the system was allowed to stand for 50 minutes before the sampling of approximately 10 ml of the reaction medium.
  • Quenching of the sample was carried out by the introduction of 1 ml of methanol. The resulting mixture was discarded for further analysis. After sampling, a new charge of 0.32 ml of isobutylene was added in the reactor kept at -50°C. The concentration of monomer units (previous polymer + new charge) was then 0.15 mole/I. The system was allowed to stand at -50 ⁇ C for a new period of 50 minutes and quenched. The sample was then treated by 10 ml of heptane filtrated to eliminate catalyst residues and concentrated. The final polymer, containing the polymer produced after the introduction of the second charge of monomer, was collected by precipitation in acetone, filtrated and dried under secondary vacuum to constant weight.
  • the yield was considered as complete and the polymer was analysed by NMR and infrared spectroscopy and size exclusion chromatography (SEC).

Abstract

L'invention se rapporte à un procédé de synthèse directe par polymérisation cationique vivante de nouveaux matériaux polymères fonctionalisés par des groupes fonctionnels contenant de l'azote, tels que des groupes terminaux azido, cyano, carbonylamino, cyanato, thiocyanato ou thiocarbonylamino. La polymérisation et la fonctionalisation ont lieu de manière sensiblement simultanée. Tous les réactants nécessaires destinés à la fonctionalisation sont présents lorsque la polymérisation est déclenchée. Le groupe fonctionnel contenant de l'azote est produit comme une partie d'une molécule possédant une fraction de libération qui est de préférence stabilisée à la résonance, ou un type alkyle tertiaire, et qui agit afin d'aider l'espèce contenant l'azote à fonctionner comme un groupe labile.
PCT/US1993/011918 1992-12-17 1993-12-08 Synthese directe par polymerisation cationique vivante de polymeres contenant de l'azote WO1994013706A1 (fr)

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WO2002028913A2 (fr) * 2000-10-06 2002-04-11 Carnegie Mellon University Procede de polymerisation de monomeres ioniques
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US9644042B2 (en) 2010-12-17 2017-05-09 Carnegie Mellon University Electrochemically mediated atom transfer radical polymerization
US8969484B2 (en) 2011-07-08 2015-03-03 Chevron Oronite Company Llc Methods of producing mono- and multi-functional polymers from terpene-based initiators
US10072042B2 (en) 2011-08-22 2018-09-11 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
US9533297B2 (en) 2012-02-23 2017-01-03 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
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